WO2002032977A1 - Water-dispersible polyisocyanate composition, process for its production, water-base curable composition and its application - Google Patents

Abstract

A water-dispersible polyisocyanate composition which comprises a hydrophobic polyisocyanate (A) and a vinyl polymer (B) bearing both a nonionic group and an isocyanate group and is characterized in that the polyisocyanate (A) can be dispersed in an aqueous medium by virtue of the vinyl polymer (B). The composition can be produced by reacting a hydrophobic polyisocyanate with a vinyl polymer (b) bearing a nonionic group and an active hydrogen containing group reactive with an isocyanate group at a molar ratio of isocyanate group to the active hydrogen containing group of 3 to 350.

Description

 Description Water-dispersible polyisocyanate composition, its production method,

 Aqueous curable composition and its application

 The present invention relates to a water-dispersible polyisocyanate composition useful in the industrial fields such as paints, adhesives, and fiber processing agents, an aqueous curable composition containing the polyisocyanate composition, and applications thereof. About. More specifically, a water-dispersible polyisocyanate composition containing a polyisocyanate and a specific vinyl polymer useful for various applications such as aqueous paints, adhesives, binders, and impregnating agents, and aqueous curing The present invention relates to a composition, a water-based paint, and a water-based adhesive. Background art

 In recent years, there has been a strong demand for reducing the amount of volatile organic solvents used due to environmental issues. To meet this demand, attempts have been made in many fields to make aqueous compositions of organic solvent-based compositions containing polyisocyanates. For example, Japanese Patent Publication No. 55-7472, U.S. Pat. No. 5,252,966 (Japanese Patent Application Laid-Open No. 5-222150) include a part of polyisocyanate. A polyisocyanate composition is described which is modified with polyoxyalkylene glycol having one end capped with an alkoxy group. When such a composition is dispersed in water, there is a problem that a reaction between water and an isocyanate group contained in the polyisocyanate easily occurs, and the isocyanate group is easily consumed by water. A curable composition comprising such a polyisocyanate composition and an aqueous resin having an active hydrogen group-containing group has a short pot life, and a cured product obtained from such a curable composition has hardness and water resistance. There are inferior drawbacks.

Japanese Patent Application Laid-Open No. Hei 7-113005 discloses a polyoxyalkylene glycol in which a part of an isocyanate group contained in a polyisocyanate is blocked at one end with an alkoxy group, and an aliphatic group containing a hydroxyl group. A polyisocyanate composition having improved water dispersibility obtained by modification with a compound or a fatty acid ester is described. It is listed. In a dispersion obtained by dispersing the polyisocyanate composition in water, the stability of the isocyanate group in water is somewhat improved, but the dispersibility in water is insufficient and workability is poor. Further, the curable composition comprising the polyisocyanate composition and the aqueous resin having an active hydrogen group-containing group has a problem that the pot life is short and the obtained cured product is inferior in hardness and water resistance.

 JP-A-9-71720 discloses that an ionic emulsifier is added to a polyisocyanate obtained by modifying a part of an isocyanate group with a polyoxyalkylene glycol whose one end is blocked with an alkoxy group. A polysocyanate composition to which is added. In such a composition, the water dispersibility and the stability of the isocyanate group in water are somewhat improved, but not to a satisfactory level. Further, since the composition comprising such a polyisocyanate composition and an aqueous resin having an active hydrogen group-containing group contains an ionic emulsifier, the resulting cured product has a drawback of poor hardness and water resistance. Japanese Patent Application Laid-Open No. Hei 11-16871 discloses a polyoxyalkylene glycol in which one end is blocked with an alkoxy group, a higher alcohol having 8 or more carbon atoms, and a fatty acid having 8 or more carbon atoms. A method for dispersing a polyisocyanate using an isocyanate group-free dispersant obtained by reacting the above-mentioned fatty acid ester containing an active hydrogen group-containing group and polyoxypropylene monoalkyl ether is disclosed. Have been.

 Also, Japanese Patent Application Laid-Open No. 9-104814 discloses a polyisoalkylene glycol containing a polyoxyalkylene glycol having one end blocked with an alkoxy group and a group containing an active hydrogen atom such as a higher alcohol. A polyisocyanate composition comprising a polyisocyanate and an isocyanate group-free dispersant obtained by reacting a contained aliphatic compound is disclosed. A composition obtained by the method disclosed in Japanese Patent Application Laid-Open No. 1-1678716 or a composition disclosed in Japanese Patent Application Laid-Open No. In this case, the stability of the isocyanate group in water is relatively good. However, since the composition comprising the polyisocyanate composition and the aqueous resin having an active hydrogen group-containing group contains a dispersant having no isocyanate group, the resulting cured product has poor compatibility and appearance and hardness. However, there is a drawback of poor water resistance.

Japanese Patent Application Laid-Open No. 6-23995F discloses that a part of the polyisocyanate is partially terminated. A polyisocyanate composition comprising a polyisocyanate modified with a polyoxyshethylene glycol blocked with a alkoxy group and an acryl-based polymer having an isocyanate group is described. In such a composition, the stability of the isocyanate group to water is insufficient, and a curable composition comprising an aqueous resin having the polyisocyanate composition has a short pot life, and the obtained cured product also has There is a problem with poor water resistance.

 Japanese Unexamined Patent Publication No. 2000-191743 discloses a polyisocyanate composition obtained by modification with an ionic surfactant containing active hydrogen and a nonionic surfactant containing active hydrogen. Is disclosed. In such a composition, the water dispersibility is good, but the stability of the isocyanate group in water is insufficient. Further, the curable composition comprising such a composition and an aqueous resin having an active hydrogen group-containing group has a drawback that the pot life is short and the hardness and water resistance of the cured product are poor.

 An object of the present invention is to solve various problems in the prior art as described above, and to provide water having excellent dispersibility in water, stability in water, compatibility with an aqueous resin having an active hydrogen group-containing group, and the like. To provide a dispersible polysocyanate composition; to provide an aqueous curable composition comprising the polysocyanate composition and water, which is excellent in water stability and curability; and to provide the polyisocyanate composition and an active hydrogen group. It is an object of the present invention to provide a water-based curable composition comprising a water-based resin having a containing group, which has a long pot life, is excellent in curability, and gives a cured product excellent in appearance, water resistance and hardness. An object of the present invention is to provide an aqueous paint containing an aqueous cured composition and an aqueous adhesive. Disclosure of the invention

Thus, the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a composition comprising a vinyl polymer containing a nonionic group and an isocyanate group and a hydrophobic polyisocyanate has been found to be soluble in water. It is excellent in dispersibility, and in a water dispersion obtained by dispersing in water, the isocyanate group has good stability to water, and the water dispersion has a long pot life and excellent curability; Furthermore, the composition comprising the polysuccinate composition and the aqueous resin having an active hydrogen group-containing group has a long pot life and excellent curability, and the composition has an appearance, hardness, water resistance and the like. Excellent The present invention has been found to give a cured product that can be obtained.

 That is, the present invention comprises a hydrophobic polyisocyanate (A) and a vinyl polymer (B) containing a nonionic group and an isocyanate group, wherein the hydrophobic polyisocyanate is contained in an aqueous medium. It is an object of the present invention to provide a water-dispersible polyisocyanate composition capable of dispersing the acrylate (A) with the vinyl polymer (B) having the nonionic group and the isocyanate group.

 The present invention also relates to the present invention, wherein the hydrophobic polyisocyanate and a vinyl polymer (b) containing a nonionic group and an active hydrogen group-containing group which reacts with an isocyanate group are combined with an isocyanate group Z An object of the present invention is to provide a method for producing a water-dispersible polyisocyanate composition, characterized in that active hydrogen group-containing groups are reacted at a molar ratio of 3 to 350.

 Further, the present invention provides an aqueous curable composition comprising the above water-dispersible polyisocyanate composition and an aqueous resin (C) or water. Further, the present invention provides an aqueous paint containing the above-mentioned aqueous curable composition and an aqueous adhesive containing the above-mentioned curable composition. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in more detail.

 First, the water-dispersible polyisocyanate composition of the present invention will be described.

 The water-dispersible polysocyanate composition of the present invention contains a hydrophobic polysocyanate (A) and a vinyl polymer (B) containing a nonionic group and an isocyanate group. In addition, in the water-dispersible polyisocyanate composition of the present invention, the vinyl polymer (B) having a nonionic group has an ability to disperse the hydrophobic polyisocyanate (A) in an aqueous medium. Have.

The hydrophobic polyisocyanate (A) used in the present invention refers to a polyisocyanate having no hydrophilic groups such as various known and commonly used anionic groups, cationic groups and nonionic groups in the molecule. Representative examples of such a hydrophobic polyisocyanate (A) include 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, and 1,6-hexamone. Tylene diisocyanate. 1, 1 2—Dodecamethylene diisocyanate, 2, 2, 4— or 2, 4, 4— Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanatoto 41-isocyanatomethyloctane, 2-isocyanatoethyl (2,6-diisocyanate) aliphatic triisocyanate such as hexanoate;

1,3_ or 1,4-bis (isocyanatomethylcyclohexane), 1,3-1, or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl

(3-isocyanatomethyl) cycloaliphatic diisocyanate such as cyclohexyl isocyanate, dicyclohexylmethane-1,4,4'-diisocyanate, 2,5- or 2,6-diisocyanato-methyl norbornane; 2,5 —Or an alicyclic triisocyanate such as 2,6-diisocyanatomethyl-2-isocyanate propyl norbornane; m-xylylene diisocyanate, hi,, ', a' — 亍 tramethyl-m_xylylenedi M- or p-phenylene diisocyanate, such as socyanate; m- or p-phenylenediisocyanate, tolylene-1,4_ or 2,6-diisocyanate, diphenylmethane-1,4,4'-diisocyanate N, naphthalene 1,5-diisocyanate, diphenyl 1,4'-diisocyanate, 4,4 'diisocyanate 1,3,3'-dimethyl Diphenyl, 3-methyl-diphenylmethane-1,4,4'-diisocyanate, diphenylether —4,4'-Aromatic diisocyanate such as diisocyanate; triphenyl methanetriisocyanate, tris (isocyanatophenyl) thiophosphene An aromatic trisocyanate as described above; a diisocyanate or a polyisocyanate having a retdione structure obtained by cyclizing and dimerizing isocyanate groups of various diisocyanates or triisocyanates as described above; Polyisocyanate having an isocyanurate structure obtained by cyclizing and trimerizing the isocyanate groups of diisocyanate or triisocyanate; various diisocyanates or triisocyanates as described above are mixed with water A polyisocyanate having a bullet structure obtained by the reaction; a polyisocyanate having an oxadiazine trione structure obtained by reacting various kinds of diisocyanate or triisocyanate as described above with carbon dioxide; and a polyisocyanate having an arophanate structure And isocyanate. Among them, fatty acid is preferred in terms of stability of isocyanate groups in water, and weather resistance of a coating film when a curable composition containing a water-dispersible polyisocyanate composition is used as a coating material. Aromatic or alicyclic diisocyanates, triisocyanates, aralkylenediisocyanates, or polyisocyanates derived therefrom are preferred. Among these polyisocyanates, in order to obtain an aqueous curable composition having excellent weather resistance and durability, an isocyanurate-type polyisocyanate, a polyisocyanate having a burette structure, and a uretdione structure are required. Or a polyisocyanate having an aromatic structure, and a polyisocyanate having three or more functions, such as a polyisocyanate obtained by reacting a diisocyanate with a trihydric or higher polyhydric alcohol.

 In addition to the hydrophobic polyisocyanate (A), a polyisocyanate having a hydrophilic group can be used in combination within a range that does not impair the water stability of the water-dispersible polyisocyanate composition of the present invention.

 A typical example of the vinyl polymer containing a nonionic group and an isocyanate group (B) [hereinafter referred to as an NCO group-containing vinyl polymer (B)] used in the present invention is an acrylic polymer. And fluorinated olefin-based polymers, vinyl ester-based polymers, aromatic vinyl-based polymers and polyolefin-based polymers. Among them, when the water-dispersible polyisocyanate composition of the present invention is used as a curing agent and an acrylic polymer is used as a base resin, acrylic polymer and fluorophore are compatible in terms of compatibility. In-based polymers are preferred.

As the nonionic group introduced into the NCO group-containing vinyl polymer (B), there are various known and commonly used nonionic groups, and the preferred one is an alkoxy group having a terminal, a substituted alkoxy group, an ester group, or a carbamate group. And polyoxyalkylene groups blocked with various groups. Representative examples thereof include various polyoxyalkylene groups such as a polyoxyethylene group, a polyoxydipropylene group or a polyoxybutylene group, and the above-mentioned oxy groups such as a poly (oxyethylene-l-oxypropylene) group. Those obtained by random copolymerization of alkylene moieties, those obtained by combining different polyoxyalkylene groups such as polyoxyethylene-polyoxypropylene groups in blocks, and ring-opening polymerization of dioxolane rings. And the like. Preferred among these polyoxyalkylene groups are those containing oxyethylene units as essential constituent units.

 Among the groups used for the terminal blocking described above, preferred are an alkoxy group and a substituted alkoxy group, and particularly preferred is an alkoxy group. Representative examples of the alkoxy group include a lower alkoxy group such as a methoxy grave, an ethoxy group, and a butoxy group.

 The number average molecular weight of the polyoxyalkylene group is from about 130 to about 10,000 in view of the water dispersibility of the polyisocyanate composition and the curability of the aqueous curable composition containing the composition. Of these, preferably within the range of 150 to 6,000, and most preferably within the range of 200 to 2,000.

 The suitable amount of the nonionic group introduced into the NCO group-containing vinyl polymer (B) is such that the hydrophobic polyisocyanate (A) can be easily dispersed in water and the polyisocyanate composition of the present invention can be used. The amount may be within a range that does not impair the stability of the isocyanate group contained in the dispersion obtained by dispersing in water. The preferable amount is 8 to 80% by weight of the NCO group-containing vinyl polymer (B), more preferably 12 to 65% by weight, and most preferably 1 to 65% by weight. 5 to 55% by weight.

 As the isocyanate group introduced into the NCO group-containing vinyl polymer (B), there are various well-known and commonly used isocyanate groups. Representative examples thereof include an isocyanate group bonded to an alkyl group and a cycloalkyl group. An isocyanate group bonded to an alkyl group substituted with an aryl group, an isocyanate group bonded to an alkyl group substituted with a cycloalkyl group, an isocyanate group bonded to an alkyl group substituted with an aryl group, and the like. Can be

 The preferred amount of isocyanate to be introduced into the NCO group-containing vinyl polymer (B) is such that the NCO group-containing vinyl polymer (B) is an aqueous resin having an active hydrogen group-containing group.

(C) an active hydrogen or water capable of participating in crosslinking by reacting with water and in an amount which does not impair the stability of the water-dispersible polyisocyanate composition of the present invention. The preferable amount is 0.05 to 6 mol, preferably 0.1 to 5.0 mol, per 1,000 g of the NCO group-containing vinyl polymer (B). Preferably, it is 0.2 to 4.0 mol.

 In the water-dispersible polyisocyanate composition of the present invention, the NCO group-containing vinyl polymer (B) has the ability to disperse the hydrophobic polyisocyanate (A) in water. Therefore, the NCO group-containing vinyl polymer (B) has a function of imparting excellent dispersibility in water to the polyisocyanate composition of the present invention. Further, the NCO group-containing vinyl polymer (B) imparts water stability of the isocyanate group contained in the aqueous dispersion of the composition. Further, since the NCO group-containing vinyl polymer (B) also has an isocyanate group, the aqueous resin having an active hydrogen group-containing group described below is used.

The aqueous curable composition of the present invention comprising (C) or water and a polyisocyanate composition has excellent curability. The aqueous curable composition gives a cured product having excellent performance.

 Further, when a hydrophobic group having a total of 4 or more carbon atoms is introduced into the NCO group-containing vinyl polymer (B), the polyisocyanate composition of the present invention imparts more excellent water dispersibility. In addition, it is preferable in that the stability of the isocyanate group contained in the aqueous dispersion of the composition in water can be further improved.

 Typical examples of the hydrophobic group having 4 or more total carbon atoms introduced into the NCO group-containing vinyl polymer (B) include n-butyl group, iso-butyl group, tert-butyl group, and n-butyl group. An alkyl group having 4 or more carbon atoms, such as a pentyl group, an n-hexyl group, a 2-ethylhexyl group, an η-octyl group, an η-dodecyl group or an η-tactadecyl group; a cyclobutyl group A cycloalkyl group having 4 or more carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a dicyclopentanyl group, a bornyl group, an isobornyl group; a cyclopentylmethyl group, a cyclohexylmethyl group, 2 An alkyl group substituted by a cycloalkyl group such as —cyclopentylethyl group or 2-cyclohexylethyl group; phenyl, 4-methylphenyl or 1-naphthyl Can, total carbon atoms is 6 or more Ariru or substituted Ariru group; more, such as benzyl or 2-Fueniruechiru group, Araru kill group, and the like.

Among the various hydrophobic groups having a total number of carbon atoms of 4 or more as described above, those having a total carbon number of 4 to 22 are preferable, and those having a total carbon number of 4 to 22 are particularly preferable. It has 5 to 18 children. Particularly preferred among such hydrophobic groups are an alkyl group, a cycloalkyl group or an alkyl group substituted with a cycloalkyl group.

 When introducing a hydrophobic group having a total of 4 or more carbon atoms into the NCO group-containing vinyl polymer (B), the preferable amount of introduction is as follows. The weight ratio of the hydrophobic group is 1 to 45 weight. /. And preferably 5 to 30% by weight.

 The above-mentioned NCO group-containing vinyl polymer (B) has an isocyanate group in the molecule, and further has a reactive functional group such as a blocked active hydrogen group-containing group, an epoxy group or a hydrolyzable silyl group. It is preferably introduced into the group-containing vinyl polymer (B). Since these reactive functional groups participate in the crosslinking reaction together with the isocyanate group, the curability of the aqueous curable composition of the present invention can be improved, and a cured product having more excellent performance can be obtained.

Representative examples of the blocked active hydrogen group-containing group include a blocked hydroxyl group, a blocked carboxyl group, a blocked amino group, and the like. Among such blocked active hydrogen group-containing groups, typical examples of the blocked hydroxyl group include a trimethylsilyl ether group, a triethylsilyl ether group, a dimethylcyclohexylsilyl ether group, and a dimethyl-tert-butylsilyl group. A hydroxyl group blocked with a triorganosilyl group such as an ether group; and an S-unsaturated ether compound such as methyl vinyl ether, ethyl vinyl ether, 2-methoxypropene, dihydrofuran, dihydroxypyran, etc. added to the hydroxyl group. Examples of blocked carboxyl groups include acetal or ketal obtained by the reaction. Representative examples of blocked carboxyl groups include trimethylsilyl ester groups, triethylsilyl ester groups, dimethylcyclohexylsilyl ester groups, and dimethyl groups. carboxyl groups blocked as triorganosilyl esters such as tert-butylsilyl ester groups; carboxyl groups such as methyl vinyl ether, ethylvinyl alcohol, 2-methoxypropene, dihydrofuran, and dihydropyran; Carboxy blocked as a hemiacetal ester or hemiketal ester obtained by adding an unsaturated ether compound And a sil group.

 Representative examples of blocked amino groups include bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, and bis (triorganosilyl) amino groups such as bis (dimethyl-tert-butylsilyl) amino group. An amino group blocked as an amino group; an amino group blocked as an aldimine obtained by reacting an amino compound with an aldehyde compound such as formaldehyde, acetoaldehyde, propionaldehyde, and n-butyraldehyde; an amino group and an acetone, An amino group blocked as a ketimine obtained by reacting with a ketone compound such as a ketone or methyl isobutyl ketone; an aldehyde compound or a ketone as described above as used for converting an amino group into an aldimine or a ketimine. Compound The 2-§ amino alcohols with amino group and proc as Okisazorijin obtained by reacting the like.

 Among the various blocked active hydrogen group-containing groups described above, a hydroxyl group blocked with a triorganosilyl group is particularly preferred. Since the hydroxyl group blocked by the triorganosilyl group has hydrophobicity, the polyisocyanate composition of the present invention is introduced by introducing such a group into the NCO group-containing vinyl polymer (B). Further excellent water dispersibility can be imparted, and the stability of the isocyanate group contained in the aqueous dispersion of the polyisocyanate composition can be further improved.

 Representative examples of the epoxy group include a glycidyl group, a methylglycidyl group, an epoxycyclohexyl group, and the like.

Among the above functional groups, the hydrolyzable silyl group is an alkoxy group, a substituted alkoxy group, a phenoxy grave, an iminooxy group, an alkenyloxy group, which is a group which is eliminated by hydrolysis to form a hydroxyl group bonded to a hydrogen atom. And a silyl group to which a hydrolyzable group such as a halogen atom is bonded. Among these silyl tombs, particularly preferred are alkoxysilyl groups to which an alkoxy group or a substituted alkoxy group is bonded as a hydrolyzable group. Typical examples of alkoxysilyl tombs include trimethoxysilyl, triethoxysilyl, triη-propoxysilyl, triη-butoxysilyl, methyldimethoxysilyl, and methyl. Examples include a dimethoxysilyl group, a dimethylmethoxysilyl group, and a tris (2-methoxetoxy) silyl group.

 Among the above-mentioned reactive functional groups to be introduced into the NCO group-containing vinyl polymer (B), particularly preferred are a blocked active hydrogen group-containing group and an epoxy group.

 When the functional groups such as the blocked active hydrogen group-containing group, epoxy group, and hydrolyzable silyl group are introduced into the NCO group-containing vinyl polymer (B), the amount of these functional groups introduced is From the viewpoint of the water dispersibility of the polyisocyanate composition of the present invention and the curability of the aqueous curable composition of the present invention, 0.05 to 100% of the NCO group-containing vinyl polymer (B) per 100 g of the vinyl polymer (B). 2 mol, preferably 0.1 to 1 mol.

 The weight average molecular weight of the NCO group-containing vinyl polymer (B) is determined based on the dispersibility in water of the water-dispersible polyisocyanate composition of the present invention and the water content of the isocyanate group contained in the aqueous dispersion of the composition. From the viewpoints of the stability to water and the curability of the aqueous curable composition of the present invention, it is from 5,000 to 200,000, more preferably from 8,000 to 70,000.

 To prepare the NCO group-containing vinyl polymer (B), (1) a vinyl polymer containing a hydrophobic polyisocyanate and a previously prepared nonionic group and an active hydrogen group-containing group that reacts with the isocyanate group. The following methods can be applied: a method of reacting with a coalescing compound [hereinafter referred to as method (1)], a method of (2) a method of copolymerizing a vinyl monomer containing an isocyanate group [hereinafter referred to as method (2)], or the like. .

 Hereinafter, the method (1) will be described.

 The method (1) comprises a vinyl polymer having an active hydrogen group containing a hydrophobic polyisocyanate, a nonionic grave, and an active hydrogen group that reacts with an isocyanate group (hereinafter referred to as an active hydrogen group-containing vinyl polymer (b)). Is reacted in a molar ratio in which the isocyanate group is excessive with respect to the active hydrogen group-containing group.

In the method (1), as the hydrophobic polyisocyanate, the same one as the above-mentioned hydrophobic polyisocyanate (A) can be used. Then, a polyisocyanate having a hydrophilic group can be used in an amount within a range that does not impair the stability of the water-dispersible polyisocyanate composition of the present invention. In the method (1), the hydrophobic polyisocyanate and the active hydrogen group-containing vinyl polymer (b) are mixed such that the ratio of the isocyanate group and the active hydrogen group-containing group is about 1.5-3. When reacted, the reaction mixture contains the NCO group-containing vinyl polymer (B) as a main component and unreacted hydrophobic polyisocyanate as a minor component. The water-dispersible polyisocyanate composition of the present invention can be obtained by mixing the thus-prepared reaction mixture and the hydrophobic polyisocyanate (A).

 In the method (1), the hydrophobic polyisocyanate and the active hydrogen group-containing vinyl polymer (b) are reacted so that the ratio of the isocyanate group to the active hydrogen group-containing group is about 3 to 350. Then, a reaction mixture containing more unreacted hydrophobic polyisocyanate and the NCO group-containing vinyl polymer (B), that is, the water-dispersible polyisocyanate of the present invention is prepared in one step. Hereinafter, the method of the present invention for producing the water-dispersible polyisocyanate composition of the present invention by such a one-step reaction will be described.

 In preparing the water-dispersible polyisocyanate composition from the hydrophobic polyisocyanate and the active hydrogen group-containing vinyl polymer (b), the molar ratio of the isocyanate group and the active hydrogen group-containing group is 3 to 350. It is necessary to react both components within a certain range. From the viewpoint of the water dispersibility of the obtained polyisocyanate composition and the curability of the curable composition containing the composition, a range of 5 to 300 is preferable, The range of 10 to 250 is more preferable, and the range of 15 to 100 is most preferable.

 To react the hydrophobic polyisocyanate with the active hydrogen group-containing vinyl polymer (b), (1) charge and react both components together; (2) add the active hydrogen group-containing vinyl polymer to the hydrophobic polyisocyanate. Various methods can be applied, such as reacting while adding the solution of the coalesced (b), and (3) reacting while adding the hydrophobic polyisocyanate to the solution of the active hydrogen group-containing vinyl polymer (b).

Of these, methods (1) and (2) are preferable from the viewpoint of suppressing the formation of a gel. In performing the reaction of the two components, the mixture of the two components was left for a long time at a relatively low temperature of about 10 to 50 ° C. in an inert gas atmosphere. Although stirring may be carried out for a long time, it is preferable to heat and stir at a temperature of about 50 to 130 ° C for about 0.5 to 20 hours. In carrying out such a reaction, various conventional catalysts that promote the reaction between the isocyanate group and the group containing an active hydrogen group may be added.

 When preparing the active hydrogen group-containing vinyl polymer (b), a hydrophobic polyisocyanate is used instead of a part of the solvent or the whole amount of the solvent, and the active hydrogen group-containing vinyl polymer is used. The water-dispersible polyisocyanate composition of the present invention can also be prepared by allowing the preparation of (b) and the reaction of the active hydrogen group-containing vinyl polymer (b) and the polyisocyanate to proceed in parallel.

 A mixture obtained by further adding a hydrophobic polyisocyanate (A) to the water-dispersible polyisocyanate composition prepared as described above is also referred to as the water-dispersible polyisocyanate composition of the present invention. Can be used.

 Hereinafter, the vinyl polymer (B) containing an active hydrogen group used in preparing the NCO group-containing vinyl polymer (B) or the water-dispersible polyisocyanate composition of the present invention by the method (1) will be described. Will be described.

 Examples of the active hydrogen group-containing group which reacts with the isocyanate group introduced into the active hydrogen group-containing vinyl polymer (b) include various well-known and commonly used groups. Typical examples thereof include a hydroxyl group and a hydroxyl group. Carboxyl group, phosphoric acid group, phosphorous acid group, sulfonic acid group, sulfinic acid group, mercapto group, silanol group, active methylene group, force bamate group, peridode group, carboxylic acid amide group, sulfonic acid amide group, etc. Is mentioned. Of these, a hydroxyl group, an amino group, a carboxyl group and an active methylene group are preferred in terms of ease of introduction, and particularly preferred are a hydroxyl group and a carboxyl group. Each of these various types of active hydrogen group-containing groups may be introduced alone, or two or more of them may be introduced.

 In order to introduce the above-mentioned active hydrogen group-containing group into the vinyl polymer (b), various known and commonly used methods can be applied, but the above-mentioned vinyl monomer having an active hydrogen group-containing group is copolymerized. It is easy to introduce by introducing.

A representative example of a hydroxyl-containing monomer used in preparing the vinyl polymer containing active hydrogen (b) is 2-hydroxyhexyl (meth) acrylate. 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (2-hydroxymethyl) acrylate , Ethyl (2-hydroxymethyl) acrylate, butyl (2-hydroxydimethyl) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, glycerin mono (meth) acrylate, monophthalic acid (2- (Hydroxypropyl) mono- [2- (meth) acryloyloxy] ethyl ester, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylates containing a hydroxyl group, such as polyethylene; polyethylene Glycol mono (me Mono (meth) acrylates of hydroxyl-containing polyoxyalkylene glycols such as acrylates, polypropylene glycol mono (meth) acrylates, and polybutylene glycol mono (meth) acrylates; aryl alcohols, 2-hydroxyhexylaryl Hydroxyl group-containing aryl compounds such as ethers; 2-hydroxyl-vinyl alcohol, 4-hydroxybutyl vinyl ether, 6-hydroxy vinyl ether compounds containing hydroxyl groups such as xyhexylvinyl ether; N- Unsaturated carboxylic acid amide compounds having a hydroxyl group such as methylol (meth) acrylamide and N-methylolcrotonate amide; hydroxyl-containing unsaturated fatty acids such as ricinoleic acid; hydroxyl-containing unsaturated such as alkyl ricinoleate Fatty acid esters Monomer obtained hydroxyl group-containing monomer rest of as mentioned above various Te because Shi allowed addition reaction with epsilon _ force Puroraku tons and the like. These may be used alone or in combination of two or more.

Representative monomers having a carboxyl group as an active hydrogen group-containing group include (meth) acrylic acid, 2-carboxyethyl acrylate, crotonic acid, vinyl acetate, monovinyl adipate, and sebacic acid. Monovinyl, monomethyl itaconic acid, monomethyl maleate, monomethyl fumarate, mono succinate [2- (meth) acryloyloxyshethyl], Mono phthalate [2- (meth) acryloyloxyethyl], Unsaturated monocarboxylic acids such as hexahydrophthalic acid mono [2- (meth) acryloyloxyl) and sorbic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid; . Representative monomers having an amino group as an active hydrogen group-containing group include 2- (N-methylamino) ethyl (meth) acrylate, 2- (N-ethylamino) ethyl (meth) acrylate, — (Nn-butylamino) ethyl (meth) acrylate, 2- (N-tert-butylamino) ethyl methacrylate, 2- (N-methylamino) ethylcrotonate, 2- (N-ethylamino) ethylcrotonate, 2- (N-butylamino) ethyl monotonic vinyl containing a secondary amino group, such as ethyl chloroformate. These may be used alone or in combination of two or more. Representative monomers having an active methylene group as an active hydrogen group-containing group are vinylacetoacetate, 2-acetoacetoxityl (meth) acrylate, and 2-acetoacetoxypropyl (meth) acrylate. , 3-acetoacetoxypropyl (meth) acrylate, 3-acetoacetoxybutyl (meth) acrylate, 4-acetoacetoxybutyl (meth) acrylate, arylacetoacetate, 2,3-di (acetoacetoxy) ) Propyl methacrylate. These may be used alone or in combination of two or more.

 The active hydrogen group-containing group to be introduced into the active hydrogen group-containing vinyl polymer (b) is based on the water dispersibility of the polyisocyanate composition of the present invention and the isocyanate group contained in the aqueous dispersion of the composition. From the viewpoint of stability, 0.01 to 5 mol, preferably 0.05 to 3 mol, most preferably 0 to 5 mol per 100 g of the active hydrogen group-containing vinyl polymer (b). 1 to 2 moles.

 To introduce a nonionic group into the active hydrogen group-containing vinyl polymer (b), (1) copolymerize a vinyl monomer containing a polyoxyalkylene group whose terminal is blocked with an alkoxy group, (2) previously prepared For example, a method of reacting a vinyl polymer having a functional group with a polyoxyalkylene compound having a functional group reactive with the functional group and having a terminal blocked with an alkoxy group can be applied. Of these, the former method is simple and preferred.

According to the method (1), typical examples of the vinyl monomer containing a polyoxyalkylene group used in preparing the active hydrogen group-containing vinyl polymer (b) are listed above. (Meth) acrylic acid ester type, crotonic acid ester type, itaconic acid ester type having various polyoxyalkylene groups, Various monomers such as fumaric acid ester type and vinyl ether type are exemplified.

 Representative examples of (meth) acrylate monomers include monomethoxylated polyethylene glycol, monomethoxylated polypropylene glycol, or a polyester monomer having both oxyethylene and oxypropylene units. Examples include esters of various monoalkoxylated polyether diols, such as toxides, with (meth) acrylic acid.

 The amount of the nonionic group introduced into the active hydrogen group-containing vinyl polymer (b) is determined according to the present invention, which is obtained by reacting the active hydrogen group-containing vinyl polymer (b) with the hydrophobic polyisocyanate. The amount may be such that the polyisocyanate composition is easily dispersed in water, and the stability of the isocyanate groups contained in the dispersion obtained by dispersing the composition in water is not impaired. The preferred amount is from 10 to 90% by weight of the active hydrogen group-containing vinyl polymer (b), the more preferred amount is from 15 to 70% by weight, and the most preferred amount is It is 20 to 60% by weight.

 By introducing a hydrophobic group having a total carbon number of 4 or more into the active hydrogen group-containing vinyl polymer (b), an NCO group-containing vinyl polymer having a hydrophobic group having a total number of 4 or more carbon atoms is obtained. It is possible to obtain a coalesced (B), and as described above, imparts more excellent dispersibility in water to the polyisocyanate composition of the present invention, and disperses the isocyanate group contained in the aqueous dispersion of the composition with respect to water. At any time, stability can be improved. In order to introduce a hydrophobic group having a total carbon number of 4 or more into the active hydrogen group-containing pinyl polymer (b), a vinyl monomer having such a group may be copolymerized.

Typical examples of the vinyl monomer having a hydrophobic group having 4 or more total carbon atoms as described above include n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and tert-butyl methacrylate. It has an alkyl group having a total carbon number of 4 to 22 such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, etc. Meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Various types Cycloalkyl (meth) acrylates; cyclopentylmethyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, 2-cyclohexylethyl

Cycloalkylalkyl (meth) acrylates such as (meth) acrylate; various aralkyl (meth) acrylates such as benzyl (meth) acrylate or 2-phenylethyl (meth) acrylate; styrene, p-tert-butylstyrene Various aromatic vinyl-based monomers, such as styrene, methyl styrene, and vinyl toluene; vinyl esters of carboxylic acids having a total number of carbon atoms of 5 or more, such as vinyl bivarate, vinyl versatate or vinyl benzoate Various octanoic acid esters having an alkyl group having 4 to 22 carbon atoms, such as mono-n-butyl crotonate and 1,2-ethylhexyl crotonate; di-n-butyl maleate; 4 carbon atoms such as di-n-butyl fumarate and di-n-butyl itaconate Various unsaturated dibasic acid esters having at least 1 to 22 alkyl groups; alkyl groups having 4 to 22 carbon atoms, such as n-butyl vinyl ether and n-hexyl vinyl ether; And various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and 4-methylcyclohexyl vinyl ether.

 When a hydrophobic group having a total carbon number of 4 or more is introduced into the active hydrogen group-containing vinyl polymer (b), the suitable amount thereof is determined by the water dispersibility and the water dispersibility of the polyisocyanate composition of the present invention. From the viewpoint of the stability of the isocyanate group contained in the aqueous dispersion of the composition, the weight ratio of the hydrophobic group contained in the vinyl polymer (b) is 1 to 50% by weight <½, preferably , 5 to 30% by weight.

 In order to introduce a blocked active hydrogen group-containing group, an epoxy group, or a hydrolyzable silyl group into the active hydrogen group-containing vinyl polymer (b), various known and common methods can be applied. It is convenient to introduce a vinyl monomer having a functional group by copolymerizing the vinyl monomer.

When these functional groups are introduced into the active hydrogen-bearing vinyl polymer (b), these functional groups are involved in the crosslinking reaction together with the isocyanate group, and therefore, the curability of the aqueous curable composition of the present invention is improved. be able to. Representative examples of a vinyl monomer having a hydroxyl group blocked by a triorganosilyl group include 2-trimethylsiloxethyl (meth) acrylate, 2-trimethylsiloxypropyl (meth) acrylate, and 4-trimethyl. Siloxybutyl (meth) acrylate, 2-triethylsiloxysethyl (meth) acrylate, 2-triptylsiloxypropyl (meth) acrylate or 3_triphenylsiloxypropyl (meth) acrylate, 2-trimethylsiloxyshetylbi Examples thereof include 2-ether and 4-trimethylsiloxybutyl vinyl ether. Representative examples of vinyl monomers containing a silyl ester group include trimethylsilyl (meth) acrylate, dimethyl-tert-butylsilyl (meth) acrylate, dimethylcyclohexylsilyl (meth) acrylate, and trimethylsilylcrotone. And monovinyl monomonotrimethylsilyl ester of adipic acid.

 Representative examples of a vinyl monomer containing a hemiacetal ester group or a hemiketal ester group include 1-methoxyl (meth) acrylate, 1-ethoxyxyl (meth) acrylate, and 2-methoxyl 2 — (Meth) acryloyloxypropane or 2_ (meth) acryloyloxytetrahydrofuran.

 Representative examples of vinyl monomers containing an epoxy group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, glycidyl vinyl ether, Aryl glycidyl ether and the like.

 Representative examples of the vinyl monomer having a hydrolyzable silyl grave include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, vinyl tris (2-methoxetoxy) silane, aryl trimethoxy silane,

2-trimethoxysilylethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether, 3- (methyldimethoxysilyl) propyl vinyl ether,

3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethyoxysilane, 3- (meth) acryloyl Oxypropyl Tri-n-propoxysilane, 3- (meth) acryloyloxypropyl tri-iso-propoxysilane, 3- (meth) acryloyloxypropylmethyldichlorosilane and the like.

 When a blocked active hydrogen group-containing group, an epoxy group, or a hydrolyzable silyl group is introduced into the active hydrogen group-containing vinyl polymer (b), the amount of these functional groups to be introduced is determined by the amount of the polymer of the present invention. From the viewpoint of the water dispersibility of the isocyanate composition and the curability of the aqueous curable composition of the present invention, 0.05 to 2 mol per 1 g of the active hydrogen group-containing vinyl polymer (b), Preferably, it is 0.1 to 1 mol.

 In preparing the active hydrogen group-containing vinyl polymer (b), other known and commonly used monomers copolymerizable therewith can be used in addition to the various monomers described above. Typical examples are (meth) acrylic esters having an alkyl group having 3 or less carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. Kinds; 2-Methoxyxetil

Various ω-alkoxyalkyl (meth) acrylates such as (meth) acrylate or 4-methoxybutyl (meth) acrylate; carboxylic acids having a total number of carbon atoms of 4 or less such as vinyl acetate and vinyl propionate. Vinyl esters; various carboxylic esters having an alkyl group having 3 or less carbon atoms, such as methyl tonoate or ethyl crotonate; dimethyl maleate, dimethyl fumarate, and dimethyl itaconate; Various unsaturated dibasic acid diesters having an alkyl group having 3 or less carbon atoms, such as: various vinyl monomers containing a cyano group, such as (meth) acrylonitrile and crotononitrile; vinyl fluoride , Vinylidene fluoride, tetrafluoroethylene, black trifluoroethylen, hex Various fluoroolefins, such as fluoropropylene; various chlorinated olefins, such as vinyl chloride or vinylidene chloride; various olefins, such as ethylene or propylene; ethyl vinyl ether, η-propyl vinyl ether Various alkyl vinyl ethers having an alkyl group having 3 or less carbon atoms, such as Ν, Ν-dimethyl (meth) acrylamide, Ν- (meth) acryloylmorpholine, Ν- (meth) acryloylpyrrolidine or Examples include tertiary amide group-containing vinyl monomers such as Ν-vinyl viridone. The polymerization method for preparing the above-mentioned active hydrogen group-containing vinyl polymer (b) is not limited, and various known and commonly used polymerization methods can be applied. Among them, a solution radical polymerization method in an organic solvent is particularly convenient and preferred.

 As the polymerization initiator when applying the solution radical polymerization method, various known and commonly used compounds can be used. Typical examples are 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbutyronitrile) or 2,2'-azobis (2-methylbutyronitrile), Various azo compounds; tert-butyl benzopivalate, tert-butyl benzoyl benzoate, tert-butyl butyl benzo-2-ethyl hexanoate, G-tert-butyl butyl xylide, cumenehydroxide, or Various peroxides such as diisopropyl peroxide carbonate, and the like.

 As the organic solvent, any compound can be used as long as it is a compound that is inert to the isocyanate group. Representative examples of the compound used as such a solvent include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; various esters such as ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, and methyl iso- Various ketones such as butyl ketone, methyl n-amyl ketone, and cyclohexanone; polyalkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and ethylene glycol dibutyl ether; 2-Jim Tokisheta Ethers such as methane, tetrahydrofuran and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate. These compounds may be used alone or in combination of two or more.

In using the various compounds described above as organic solvents, those having a high water content adversely affect the stability and the like of the polyisocyanate composition of the present invention. Is preferred. In addition, when a relatively high water content is used, azeotropic dehydration in which a part of the solvent is distilled off after the polymerization is completed. Dehydration may be performed by a water method or the like to reduce the water content.

 The weight average molecular weight of the vinyl polymer (b) prepared as described above depends on the dispersibility in water of the polyisocyanate composition of the present invention and the water content of the isocyanate group contained in the aqueous dispersion of the composition. From the viewpoint of the curability of the aqueous curable composition of the present invention, preferably from 3,000 to 100,000, more preferably from 5,000 to 40,000. preferable.

 Next, the above method (2), that is, a method for preparing an NCO group-containing vinyl polymer (B) by copolymerizing an isocyanate group-containing vinyl monomer will be described.

 In order to prepare the NCO group-containing vinyl polymer (B) by the method (2), it is necessary to (1) contain the isocyanate group-containing vinyl monomer and the nonionic group-containing vinyl monomer as essential components. A vinyl polymer containing an isocyanate group, obtained by polymerizing a vinyl monomer containing an isocyanate group as an essential component; For example, a method in which a polyoxyalkylene glycol whose terminal is blocked with a group such as an alkoxy group is reacted at a molar ratio in which an isocyanate group is excessive relative to a hydroxyl group can be applied. Among these, the former different method is more convenient and more preferable.

 Representative examples of the vinyl monomer containing an isocyanate group used in the method (2) include 2-isocyanatopropene, 2-isocyanatoethylvinylether, and 2-isocyanatoethylmethylether. Examples include acrylates, m-isopropenyl-phenyl, and di-dimethylbenzyl isocyanate, and reaction products of polyisocynate with a vinyl monomer having a hydroxyl group.

 In the method (2), as the vinyl-based monomer containing a nonionic group, various monomers listed above as those used in the method (1) can be used.

In preparing the NCO group-containing vinyl polymer (B) by the method (2), in addition to the vinyl monomer containing an isocyanate group and the vinyl monomer containing a nonionic group, Other monomers copolymerizable with these monomers can be used in combination. Representative examples of the other copolymerizable monomer include the above-described method. The various monomers listed above as the copolymerizable vinyl monomer in (1) can be mentioned.

 In order to introduce a hydrophobic group having a total carbon number of 4 or more into the NCO group-containing vinyl polymer (B), the hydrophobic group having a total carbon number of 4 or more described in the above method (1) is used. The vinyl group monomer having a functional group may be copolymerized so that the amount of the hydrophobic group introduced is in the above-described preferred weight ratio.

 When a functional group such as a blocked active hydrogen group-containing group, an epoxy group, or a hydrolyzable silyl group is introduced into the NCO group-containing vinyl polymer (B), the vinyl group mentioned in the above method (1) is used. The monomer may be copolymerized so that the introduction amount of the functional group becomes the preferable amount described above.

 In order to prepare the NCO group-containing vinyl polymer (B) using the above-mentioned various vinyl monomers, it is necessary to prepare the above-mentioned vinyl polymer (b) containing an active hydrogen group as the one used in preparing the vinyl polymer (b). Solution radical polymerization may be performed using the polymerization initiator and the organic solvent as described above.

 In preparing the NCO group-containing vinyl polymer (B), a part or all of the organic solvent is replaced with the hydrophobic polyisocyanate (A), and a mixture of the organic solvent and the hydrophobic polyisocyanate (A) or Hydrophobic polyisocyanate (A) can be used as a solvent.

 A mixture containing the NCO group-containing vinyl polymer (B) as the main component prepared by the method (1) and the unreacted hydrophobic polyisocyanate as a minor component, or the above method (2) The water-dispersible polyisocyanate composition of the present invention can be obtained by mixing the prepared NCO group-containing vinyl polymer (B) and the hydrophobic polyisocyanate (A). When mixing the NCO group-containing vinyl polymer (B) and the hydrophobic polyisocyanate (A), the mixing conditions are not particularly limited, but are generally from room temperature to 150 ° C, preferably The mixing may be performed at a temperature ranging from room temperature to 100 ° C.

The ratio of the hydrophobic polyisocyanate (A) to the NCO group-containing vinyl polymer (B) in the water-dispersible polyisocyanate composition of the present invention is not particularly limited. Dispersibility of the isocyanate composition in water, aqueous dispersion of the composition From the viewpoint of the stability of the isocyanate group contained in the liquid to water and the curability of the aqueous curable composition of the present invention, (A) Z (B) = 3070 to 85Z15 is preferable in terms of weight ratio, and 5050 ~ 80 20 is more preferred, and 60 40-80 / 20 is most preferred.

 As described above, (1) a method of mixing a previously prepared NCO group-containing vinyl polymer (B) and a hydrophobic polyisocyanate (A), or (2) a method of mixing an active hydrogen group-containing vinyl polymer (b) with a hydrophobic poly- isocyanate. The water-dispersible polyisocyanate composition of the present invention is prepared by a method in which both components are reacted with each other so that the molar ratio of the isocyanate group to the active hydrogen group-containing group is 3 to 350. Among these methods, the latter method (2) is preferable because the stability of the isocyanate group is higher when the obtained water-dispersible polyisocyanate composition is dispersed in water.

 Next, an aqueous curable composition containing the water-dispersible polyisocynate composition of the present invention and an aqueous resin (C) having an active hydrogen group-containing group will be described.

 The aqueous resin (C) having an active hydrogen group-containing group used in the present invention may be any resin having an active hydrogen group-containing group capable of reacting with an isocyanate group, and its form and type are not limited. . Representative examples of the active hydrogen group-containing group contained in the aqueous resin (C) include groups containing an active methylene group such as a hydroxyl group, a carboxyl group, an amino group, an amide group, and an acetoacetyl group. No. Particularly preferred of these are a hydroxyl group and a carboxyl group. Examples of the form of the aqueous resin (C) include known and common forms such as an aqueous solution type and an aqueous dispersion type such as colloidal dispersion emulsion.

Representative examples of the aqueous resin (C) include vinyl acetate resin, styrene-butadiene resin, styrene-acrylonitrile resin, acrylic resin, fluoroolefin resin, and silicon-modified vinyl resin. Copolymer, vinyl polymer such as polyvinyl alcohol; polyester resin, polyurethane resin, phenol resin, melamine resin, epoxy resin, alkyd resin, polyamide resin, polyester resin, silicon resin Synthetic resins other than vinyl polymers such as resins; and natural polymers such as animal proteins, starch, cellulose derivatives, dextrins, and arabia rubber. And preferred of these are: It is a vinyl polymer and various synthetic resins other than the vinyl polymer.

 The amount of the active hydrogen group-containing group contained in the water-based resin (C) as described above is determined in consideration of the curability of the water-based curable composition of the present invention and the water resistance of the obtained cured product. It is from 0.1 to 6 mol, preferably from 0.2 to 4 mol, most preferably from 0.4 to 3 mol, per 0.00 g. These aqueous resins (C) may be used alone or in combination of two or more.

 The preferred mixing ratio of the water-dispersible polyisocyanate composition of the present invention and the aqueous resin (C) is determined based on the curability of the curable composition and the performance of the cured product obtained from the composition. (1) the number of moles of isocyanate groups in the polyisocyanate composition;

(2) Ratio of the total number of moles of the active hydrogen group-containing group contained in the aqueous resin (C) and the blocked active hydrogen group-containing group contained in the NCO group-containing vinyl polymer (B) ( 1) (2) is preferably from 0.1 to 5, particularly preferably from 0.3 to 3, and most preferably from 0.5 to 2.

 The above-described aqueous curable composition of the present invention can be used as a clear composition containing no pigment, or can be used as a colored composition by blending various known or common organic or inorganic pigments. Can also.

 The aqueous curable composition thus prepared can be used for various fibers such as paints, adhesives, inks, waterproofing materials, sealing agents, natural fibers, synthetic fibers, glass fibers, paper impregnating agents, natural fibers, synthetic fibers. It can be used for various applications such as various fibers such as glass fibers and surface treatment agents for paper. Especially, it is preferably used as a water-based paint or a water-based adhesive. When used as a water-based paint, such a water-based paint has a long pot life, and further, from the water-based paint of the present invention, a cured coating film having excellent appearance such as transparency and gloss, water resistance, and solvent resistance can be obtained. Can be

 Furthermore, when used as a water-based adhesive, such water-based adhesive has excellent performance such as a long pot life and high adhesive strength.

If necessary, the composition may contain additives suitable for various uses, such as fillers, leveling agents, thickeners, defoamers, organic solvents, ultraviolet absorbers, antioxidants or Various well-known and commonly used additives such as a pigment dispersant can also be blended. Next, an aqueous curable composition containing the water-dispersible polycarbonate composition of the present invention and water will be described.

 The aqueous curable composition of the present invention can be obtained by mixing the water-dispersible polyisocyanate composition with water. In order to obtain such an aqueous curable composition, from the viewpoint of the stability of the isocyanate group of the composition, the curability, and the performance of the cured product obtained from the composition, the polyisocyanate composition should be used. 100 to 100 parts by weight of water, preferably 50 to 500 parts by weight of water is added to 0 parts by weight, and both may be mixed.

 The aqueous hardening composition obtained by mixing such a water-dispersible polyisocyanate composition with water can be used as a clear composition containing no pigment, and can be used as an organic or inorganic known general-purpose composition. Various pigments can be blended and used as a coloring composition. Also, if necessary, the polyisocyanate composition and the aqueous resin

Various additives and the like exemplified as those which can be added to the aqueous curable composition obtained from (C) can also be compounded and used.

 The aqueous curable composition thus prepared can be used for the same applications as the aqueous curable composition described above, but is particularly preferably used as an aqueous paint or an aqueous adhesive.

 The paint containing the water-based curable composition has a long pot life and penetrates a high-density inorganic base material, which is difficult to penetrate with ordinary water-based paints, to form a cured coating film. This coating has the function of effectively protecting the base material and has good adhesion to the top coat, so that this paint can be used as a high-performance undercoat water-based paint. In addition, this water-based paint can be used not only as an undercoat paint but also as an overcoat paint for various substrates.

 When used as a water-based adhesive, it can be used as a water-based adhesive for various uses because of a long pot life and high adhesive strength.

As the substrate on which the aqueous paint of the present invention is applied as described above, and the substrate on which the aqueous adhesive of the present invention is applied as described above, various known and commonly used substrates are used. . Among them, the most typical ones are various metal base materials, inorganic base materials, plastic base materials, inorganic fibers such as paper, synthetic fibers, natural fibers and glass fibers. Examples include fibers, fabrics, synthetic leather, natural leather, and wood-based materials.

 Among the various base materials, typical examples of the metal base material include metals such as iron, nickel, aluminum, chromium, zinc, tin, copper, and lead; stainless steel or brass; Metal alloys: Various metals or alloys as described above, and various surface-treated metals subjected to plating and chemical conversion treatment.

 In addition, the inorganic base material is a hardened material manufactured from a calcium compound such as calcium silicate, calcium aluminate, calcium sulfate, and calcium oxide; obtained by sintering a metal oxide such as alumina, silica, and zirconia. Ceramic; tiles obtained by firing various clay minerals; various types of glass. Typical examples of the cured product produced from the calcium compound include a cured product of a cement composition such as concrete or mortar, asbestos slate, a lightweight lightweight concrete (ALC) cured product, a dolomite plaster cured product, Gypsum plaster cured products, calcium silicate plates and the like can be mentioned.

 Typical examples of plastic base materials include polystyrene, polycarbonate, polymethyl methacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate, and polyethylene terephthalate. Molded product of plastic resin; molded products of various thermosetting resins such as unsaturated polyester resin, phenol resin, crosslinked polyurethane, crosslinked acryl resin or crosslinked saturated polyester resin, etc. .

 In addition, various types of base materials as described above, which are pre-coated base materials, or the base materials coated with the coating, and furthermore, the deterioration of the coated part proceeds. Such a substrate can also be used.

 These various base materials are used in various shapes such as plate, sphere, film, sheet, large-sized structure, and complex-shaped assembly, depending on the application, and are particularly limited. There is no.

Then, the water-based paint of the present invention as described above is applied to the base material as described above by brush coating, mouth coating, spray coating, dip coating, flow 'coater coating, roll' coater. The coating is performed by a known coating method such as a single coating method, and then left at room temperature for about 1 to 10 days, or in a temperature range of about 40 to about 250 ° C for about 30 seconds to about 30 seconds. By heating for about 2 hours, a cured coating film with excellent appearance and water resistance can be obtained.

 Further, the aqueous adhesive of the present invention as described above is applied to at least one of the same type of base material or a different type of base material among the above-mentioned base materials by a known and common method such as a spatula, a brush, a spray, or a roll. Then, leave it at room temperature for about 1 to 10 days, or heat it for about 5 seconds to about 2 hours in a temperature range of about 40 to about 150 ° C, as required. By applying pressure, excellent adhesive strength can be obtained. Example

Next, the present invention will be described in detail with reference examples, examples and comparative examples, but the present invention is not limited thereto. All parts and ⁰ / ο in the text are based on weight unless otherwise specified.

 First, the water-dispersible polyisocyanate composition will be described with reference to Examples and Comparative Examples. First, the polyisocyanate used in the Examples and Comparative Examples will be described.

Hydrophobic polyisocyanate (A-1)

 Hexamethylene diisocyanate (hereinafter abbreviated as HDI) -based isocyanurate-type polyisocyanate “Vaknock DN-980 SJ [Containing an isocyanate group manufactured by Dainippon Ink and Chemicals, Inc.) Rate (hereinafter abbreviated as NCO group content) 21%, average number of NCO functional groups is about 3.6, nonvolatile content 100./o]

Hydrophobic polyisocyanate (A-2)

 Burnock DN-950, an adduct type polyisocyanate of HDI and triol [manufactured by Dainippon Ink and Chemicals, Inc., obtained by removing the solvent from an ethyl acetate solution. NCO group content 17%, average number of NCO functional groups is about 3.2, nonvolatile content 100%)

Hydrophobic polyisocyanate (A-3)

Tolylene succinate and triol adduct type A “Baknock D-750” [Dainippon Ink Chemical Industry Co., Ltd., desolvated from ethyl acetate solution. NCO group content 17%, average number of NCO functional groups is about 3.4, nonvolatile content 100%)

 Reference Example 1 [Preparation of active hydrogen group-containing vinyl polymer (b)]

 A four-necked flask equipped with a stirrer, thermometer, cooling tube and nitrogen inlet tube was charged with 429 parts of ethylene glycol (JE) (hereinafter abbreviated as EDE) and heated to 110 ° C under a nitrogen stream. After the temperature was raised, 500 parts of methoxypolyethylene glycol methacrylate (containing an average of 9 peroxyl units per molecule, hereinafter abbreviated as “MP EGMA-11”), methyl methacrylate (hereinafter referred to as MMA) 300 parts, 2-hydroxyethyl methacrylate (hereinafter abbreviated as 2-HEMA) 50 parts, cyclohexyl methacrylate (hereinafter abbreviated as CHMA)

A mixed solution consisting of 150 parts, 45 parts of t-butylhydroxy-2-ethylhexanoate and 5 parts of t-butylperoxybenzoate was added dropwise over 5 hours. After dripping,

The mixture was reacted at 110 ° C for 9 hours to obtain a solution of an acrylic polymer having a nonvolatile content of 70%. Hereinafter, this is referred to as an active hydrogen group-containing vinyl polymer (b-1).

 Reference Examples 2 to 6 (Same as above)

In the same manner as in Reference Example 1 except that the monomers shown in Table 1 were used instead of 500 parts of MP EGMA-1, 300 parts of MMA, 150 parts of CHMA, and 50 parts of 2-HEMA Polymerization was performed to obtain an acrylic polymer having a nonvolatile content of 70%. Hereinafter, these are abbreviated as active hydrogen-containing vinyl polymers (b-2) to (b_6). Table 1 shows the compounding ratios of Reference Examples 1 to 6.

table 1

《Footnote to Table 1》

Each numerical value indicating the usage ratio of raw materials shall be a copy.

 "MP EGMA-2": [Methoxy PEG glycol methacrylate (containing an average of 4 per molecule of peroxyethylene units)]

 "MP EGMA_3": [Methoxy ethoxyglycol methacrylate (containing an average of 23 lioxyethylene units per molecule)]

 "MAA": methacrylic acid

"S i H EMA": 2-trimethylmethyl methacrylate "GMA": Glycidyl methacrylate

 "2-EHMA": 2-ethylhexyl methacrylate

 “4 HCHMA”: (4-hydroxymethylcyclohexyl) methyl methacrylate Reference Example 7 [Preparation of comparative dispersant (Z— “!) Used in Comparative Example]

 In the same reactor as in Reference Example 1, 239 parts of methoxypolyethylene glycol (containing an average of 12 oxyethylene units per molecule, hereinafter abbreviated as “MP EG_1J”) and 1 1 2 After stirring thoroughly at room temperature under a nitrogen stream, 180 parts of hydrophobic polyisocyanate (A-1) was added, and the mixture was stirred at room temperature for 30 minutes. The temperature was raised to C and the reaction was continued at the same temperature for 6 hours until the isocyanate group disappeared.The product was abbreviated as Comparative Dispersant (Z-1).

 Example 1 [Preparation of water-dispersible polyisocyanate composition (P-1)]

 In the same reactor as in Reference Example 1, 200 parts of the hydrophobic polyisocyanate (A-1) and 100 parts of the active hydrogen group-containing vinyl polymer (b-1) were charged, and 90 ° in a nitrogen stream. After the temperature was raised to C, the reaction was carried out with stirring at the same temperature for 6 hours to obtain a water-dispersible polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 13%. Hereinafter, this is abbreviated as a polyisocyanate composition (P-1).

 With respect to the obtained polyisocyanate composition, the dispersibility in water and the stability of the isocyanate group contained in the obtained aqueous dispersion were evaluated. The evaluation results are shown in Table 2_1.

 Examples 2 to 8 (Preparation of water-dispersible polyisocyanate composition)

Instead of 200 parts of the hydrophobic polyisocyanate (A-1) and 100 parts of the vinyl polymer (b-1), the hydrophobic polyisocyanate (A) described in Table 2-1 and active hydrogen were used. Using the group-containing vinyl polymer (b) at the ratio shown in the same table, a reaction was carried out in the same manner as in Example 1 to prepare a polyisocyanate composition. Hereinafter, these are abbreviated as polyisocyanate compositions (P-2) to (P-8). The dispersibility in water and the stability of the isocyanate group contained in the obtained aqueous dispersion were evaluated in the same manner as in Example 1 for each of the obtained polyisocyanate compositions. Table 2-1 shows the evaluation results. Indicated.

 Comparative Example 1 [Preparation of Polyisocyanate Composition (RP-1) for Comparative Example]

 In the same reactor as in Reference Example 1, 15 parts of EDE, 36 parts of MP EG-1 and 100 parts of hydrophobic polyisocyanate (A-1) were charged, and 90 ° C for 30 minutes. Then, the mixture was reacted at 90 ° C for 6 hours to obtain a non-hydrophobic polyisocyanate modified with methoxypolyethylene glycol having a nonvolatile content of 90% and an NCO group content of 12%. . Hereinafter, this is abbreviated as a polyisocyanate composition (RP-1). The dispersibility in water and the stability of the isocyanate group contained in the obtained aqueous dispersion were evaluated in the same manner as in Example 1 for the obtained polyisocyanate composition. The results of these evaluations are shown in Table 2-2.

 Comparative Example 2 [Preparation of Comparative Polyisocyanate Composition]

 In the same reactor as in Reference Example 1, 33 parts of EDE, 200 parts of hydrophobic polyisocyanate (A-1) and 100 parts of comparative dispersant (Z-1) were charged and heated to 50 ° C. The mixture was heated and stirred and mixed under a nitrogen stream for 3 hours to obtain a comparative polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 12.6%. Hereinafter, this is abbreviated as a polyisocyanate composition (RP-2). In the same manner as in Example 1, the obtained polyisocyanate composition was evaluated for dispersibility in water and stability of the isocyanate groups contained in the obtained aqueous dispersion. The results of these evaluations are shown in Table 2-2. Comparative Example 3 [Preparation of Comparative Polysocyanate Composition]

In the same reactor as in Reference Example 1, 35 parts of hydrophobic polyisocyanate (A-1), 15 parts of methoxypolyethylene glycol (containing an average of 22 oxyethylene units per molecule), and 15 parts of propylene glycol monomethyl 67 parts of ether acetate were charged, the temperature was raised to 110 ° C, and the mixture was stirred and mixed under a nitrogen stream for 3 hours. After adding 0.5 parts of p-toluenesulfonyl isocyanate, the temperature was raised to 130 ° C, and 5 parts of styrene, 5 parts of MMA, and n-butyl acrylate (hereinafter abbreviated as BA) ), 15 parts of 3-isopropenyl-1-dimethylbenzyl isocyanate, 15 parts of methoxypolyethylene glycol methacrylate (containing an average of 22 lipoxyethylene units per molecule), and 1 part of methyl A mixture consisting of 0.25 parts of styrene dimer and 1.5 parts of t-butyl peroxyisopropyl carbonate It was added dropwise over 3 hours. After the completion of the dropwise addition, the mixture was reacted at 130 ° C. for 3 hours to obtain a comparative polyisocyanate composition having an NCO group content of 6.0%. Hereinafter, this is abbreviated as a polyisocyanate composition (RP-3). For the obtained polyisocyanate composition, the dispersibility in water and the stability of the isocyanate group contained in the obtained aqueous dispersion were evaluated in the same manner as in Example 1. Table 2-2 shows the evaluation results.

Table 2-1

 Example Example Example Example Example Example Example Example Example Example

 1 2 3 4 5 6 7 8 Polyisocia

 Ρ-1P—2P—3P—4P—5P—6P—7P—8Nate composition

Polyisocia

 Α— 1 A- 1 A— 1 A— 1 A— 1 A—1 A— 2 A— 3 nate

Vinyl polymer-1 b-2 b-3 b-4 b-5 b-6-1 b-1 1 Polyisocia

 200 (200) 200 200 200 200 200 200 200 Used amount [part]

Active hydrogen group included

Vinyl polymerization

 1 00 1 00 1 00 1 00 1 00 1 00 1 00 1 00 Use of body (b)

 Amount]

 Nonvolatile

 90 90 90 90 90 90 90 90 [%]

 Contains NCO group

 1 3 1 3 1 3 1 3 1 3 1 3 1 1 1 1 Rate [%]

 Water dispersibility ◎ ◎ ◎ ® 〇 〇 ◎ 〇

 Group residual rate 92 90 95 90 88 85 93 70

 [%]

 N CO / activity

Contains hydrogen groups ¾ 37. 1 37, 13 3. 1 56. 0 24. 5 26. 5 30. 1 30. 1

 [Molar ratio]

 (A) / (B) Weight

2.0 2.0 2.0 3.0 1.1.8 1.8 2.1.9 ratio Table 2—2

 《Footnote to Table 2-1 and 2-2》

 Each numerical value indicating the usage ratio of raw materials shall be parts by weight. "Water dispersibility":

 In a 200 ml beaker, put 80 g of deionized water, add 20 g of the prepared polyisocyanate composition, keep the mixture at 30 ° C, and place the mixture in a magnetic star. Using a stirrer and a rotor (total length 30 mm, diameter 8 mm), the mixture was stirred at a stirring speed of 200 rpm, and the dispersion behavior was visually evaluated. The evaluation criteria at that time are as follows.

 ◎ Evenly dispersed 30 seconds after the start of stirring

 1 1 minute after the start of stirring

 △ Uniform dispersion 5 minutes after the start of stirring

X Disperse evenly 10 minutes after starting stirring x: not dispersed

 "Residual rate of isocyanate group":

 An aqueous dispersion of a polyisocyanate composition was prepared by performing dispersion in the same manner as in the evaluation of water dispersibility described above, except that the stirring time was changed to 10 minutes. Then, an excess of dibutylamine relative to the isocyanate group is added to a predetermined amount of the obtained aqueous dispersion. The isocyanate group in the aqueous dispersion is determined by a reverse titration method in which the remaining dibutylamine is titrated with an aqueous hydrochloric acid solution. The content was determined. The content of the isocyanate groups immediately after the preparation of the above aqueous dispersion and after 6 hours was quantified, and the stability of the NCO groups contained in the aqueous dispersion was determined based on the residual ratio of the isocyanate groups calculated by the following equation. It was evaluated for its properties. The larger the value, the better the stability of the isocyanate group. Residual rate of isocyanate group [%] = (content of isocyanate group after 6 hours Z content of isocyanate group immediately after dispersion) X 100

 “N COZ active hydrogen group-containing group [molar ratio]”: Number of moles of N CO group Number of moles of active hydrogen group-containing group

 “(A) Z (B) weight ratio”: [weight of unreacted hydrophobic polyisocyanate (A)] / [hydrophobic polyisocyanate (A) added to vinyl polymer (b)] Weight of Vinyl Polymer (B) Produced by Example] Reference Example 8 [Preparation of Aqueous Resin (C-11)]

In the same reactor as in Reference Example 1, 5 parts of “HITENOL N-08” (anionic emulsifier manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and “Emulgen 931” [nonionic emulsifier manufactured by Kao Corporation] 5 parts of deionized water and 270 parts of deionized water were added, and the temperature was raised to 80 ° C under a nitrogen stream. Then, a water solution obtained by dissolving 0.8 part of ammonium persulfate in 16 parts of deionized water was added. throw into. Further, a mixed solution consisting of 80 parts of butyl acrylate, 99 parts of methyl methacrylate, 4 parts of acrylic acid, and 17 parts of 2-hydroxyshethyl methacrylate was added dropwise over 3 hours. After dropping, let react for 2 hours, cool to 25 ° C, neutralize with 1.5 parts of 28% ammonia water, mix with 30 parts of EDE, and add non-volatile content 40%, solid hydroxyl group A hydroxyl group-containing acrylic resin emulsion having a valency of 35 was obtained. Hereinafter, this resin is abbreviated as an aqueous resin (C-11). Example 9

 The polyisocyanate composition (P-1) and the aqueous resin (C-11) were mixed with each other so that the molar ratio of the hydroxyl groups in the aqueous resin (C-11) was 1.2Z1. An aqueous curable composition was prepared by mixing 50 parts of the composition (P-1) and 500 parts of the aqueous resin (C-1). Hereinafter, this is abbreviated as the aqueous curable composition (D-1). The obtained aqueous curable composition (D-1) was immediately applied to a glass plate and a polypropylene plate (hereinafter abbreviated as PP plate) using an applicator so that the dry coating film became 60 m. It was applied on top and dried for 1 week at a temperature of 20 ° C and a humidity of 60% RH to form a cured coating. The resulting cured coating film was evaluated for compatibility, gel fraction, and water resistance. Table 3 shows the evaluation results.

 Example 10 0 to "! 7

 In these examples, in addition to the water-based resin (C-11) as the water-based resin (C), “Watersol A CD-2000” [a hydroxyl-containing acrylic resin manufactured by Dainippon Ink and Chemicals, Inc.] Aqueous resin dispersion, nonvolatile content 35%, solid content hydroxyl value 50 mg KOH g; hereinafter, this resin is abbreviated as aqueous resin (C-12)].

 As shown in Table 3, various polyisocyanate compositions were used in place of the polyisocyanate composition (P-1). Use 500 parts of the aqueous resin (C-1) or (C-2) and adjust the molar ratio of the hydroxyl group in the aqueous resin to the isocyanate group of each polyisocyanate composition to be 1.21. An aqueous curable composition was prepared by mixing the amounts of the polycarbonate compositions described in the same table. Hereinafter, the compositions thus obtained are abbreviated as aqueous curable compositions (D-2) to (D-9). Each of the aqueous curable compositions thus obtained was applied on a glass plate and a PP plate immediately after preparation in the same manner as in Example 9, and dried at a temperature of 20 ° C and a humidity of 6 Oo / oRH for 1 week. At least, a cured coating was prepared. For these, the same evaluation as in Example 9 was performed. Table 3 shows the evaluation results.

 Comparative Examples 4 to 6

When 500 parts of (C-1) or (C-2) are used as the aqueous resin (C), the molar ratio of the hydroxyl group in the isocyanate-based aqueous resin (C-11) or (C-12) is 1. Curable compositions (RD-1) to (RD-3) for comparative evaluation were prepared by mixing the amounts of each polyisocyanate composition shown in Table 3 so as to be 2/1. Immediately after the preparation, a cured coating film was prepared by coating and drying on a glass plate and a PP plate in the same manner as in Example 9. For these, the same evaluation as in Example 9 was performed. The evaluation results are shown in Table 3, Examples 18, 19, and Comparative Example 7.

After leaving D-1, D-2, and RD-1 prepared above at room temperature for 6 hours (referred to as D_1, D-2 ', and RD-1', respectively), the dried coating film was formed. It was applied on a glass plate using an applicator so as to have a length of 60 m, and was dried at a temperature of 20 ° C and a humidity of 60% RH for 1 week to form a cured coating film. For these, the same evaluation as in Example 9 was performed. Table 3 shows the evaluation results.

Table 3

 Polyisosia A * tL Holiison Water resistance of water-based resin

 Anet group Aqueous resin Use: Compatible Gel fraction White paint film Use of swelling paint composition a:

 Compounded Example 9 D—1 P-1 C-1 50 500 ◎ 94 〇 例 Example 10 D- 2 P-2 C- 1 50 500 ◎ 97 ◎

Example 1 1 D— 3 P-3 C-1 50 500 ◎ 97 ◎ ◎ Example 1 2 D— 4 P-4 C- 1 50 500 ◎ 96 〇 例 Example 1 3 D-5 P— 5 C- 1 50 500 ◎ 92 〇 実 施 Example 14 D- 6 P- 6 C- 1 50 500 〇 90 〇 △ Example 15 D-off P-- 7 C- 1 60 500 ◎ 93 〇 実 施 Example 16 D- 8 P- 8 C-1 60 500 〇 87 〇 Δ Example 1 7 D— 9 P- 1 C- 2 60 500 ◎ 92 〇 比較 Comparative Example 4 RD— 1 RP-1 C- 1 55 500 △ 83 △ X Comparative Example 5 RD-2 RP-2 C-1 52 500 X 77 XX Comparative Example 6 R D-3 RP-1 C- 2 65 500 △ 82 ΔX Example 18 D-1 P-1 C-1 50 500 ◎ 94 〇 〇 Example 1 9 D_ 2 P― 1 C― 1 50 500 ◎ 98 ◎ ◎ Comparative Example 7 RD-1 'RP― 1 C― 1 55 500 X 80 XX

《Footnote of Table 3》

 Each numerical value indicating the usage ratio of raw materials shall be parts by weight.

 "Compatibility":

 The transparency of a coating film formed on a glass plate was visually evaluated. The evaluation criteria at that time are as follows.

 ◎: no turbidity

 〇: Very slightly turbid

 Δ: quite turbid

 : Extremely cloudy

 "Gel fraction":

 The curability of the aqueous curable composition was evaluated. The coating film formed on the PP plate was cut from the PP plate, immersed in acetone at 25 ° C for 48 hours, and dried at 100 ° C for 90 minutes. The gel fraction was calculated by the following equation.

Gel fraction _[0/0] = (Weight of the coating film after the weight acetone soak the coating film before acetone soak) X 1 0 0

 "water resistant" :

 The coating film formed on the glass plate was immersed in deionized water at 25 ° C for 96 hours, and the appearance of the coating film was evaluated. The evaluation criteria at that time are as follows.

 Evaluation criteria for coating whitening

 ◎: No change

 〇: Very slight whitening

 Δ: considerably whitened

 X: Significant whitening

 Criteria for swelling of coating film

 ◎ No change

 〇 Very slight swelling

 △ Significant swelling occurred

X Significant swelling occurred. Reference Example 9 [Example of preparation of vinyl polymer (b-7)] After sufficiently replacing the air in a 2-liter stainless steel autoclave equipped with a thermometer, stirrer, and monomer injection device with nitrogen gas, 430 g of EDE was charged, and the temperature was raised to 75 ° C with stirring. did. Then, while stirring at the same temperature, 270 g of Beova 9 (vinyl ester of a branched fatty acid C9 manufactured by Shell, Netherlands), 40 g of ethyl vinyl ether, and 40 g of 4-hydroxybutyl vinyl ether 40 g, 400 g of monovinyl ether of methoxypolyethylene glycol having a polyoxyethylene group number average molecular weight of 400, 20 g of tert-butyloxypivalate, tert-butylvinyloxyethyl hexanoe A mixture consisting of 15 g of a batch and 15 g of bis (1,2,2,6,6-pentamethylpiperidine-14-yl) sebacate and 250 g of liquefied and collected chlorotrifluoroethylene For 7 hours. Further, a polymerization reaction was carried out at the same temperature for 10 hours to obtain a solution of a non-volatile group-containing fluorinated olefin polymer having a non-volatile content of 70% and a weight average molecular weight of 16,000. Hereinafter, this polymerization reaction is abbreviated as an active hydrogen group-containing vinyl polymer (b-7).

 Example 20 [Preparation of water-dispersible polyisocyanate composition (P-9)] In a reactor similar to that of Reference Example 1, 200 parts of hydrophobic polyisocyanate (A-1) and an active hydrogen group-containing compound were added. 100 parts of vinyl polymer (b_7) was charged, and the temperature was raised to 90 ° C under a nitrogen stream, and the reaction was carried out with stirring at the same temperature for 6 hours to obtain a nonvolatile content of 90% and an NCO group content of 90%. Was 13%, thereby obtaining a water-dispersible polycarbonate composition. Hereinafter, this is abbreviated as a polyisocyanate composition (P-9).

 Reference Example 10 [Preparation of aqueous resin (C-4)]

 690 g of ion-exchanged water, 15 g of sodium dodecylbenzenesulfonate, 15 g of polyoxydiethylene nonylphenol, in a 2-liter stainless steel auto crepe equipped with a thermometer, stirrer and monomer injection device 6 g of 1 ter (H LB 17) and 3 g of ammonium bicarbonate were charged and dissolved, and degassed with nitrogen. A mixture of hydroxybutyl vinyl ether (116 g), vinyl acetate (184 g), ethyl vinyl ether (200 g), and liquefied and collected 500 g of chlorofluoroethylene were placed in a pressure-resistant dropping tank.

After injecting ethylene into the autoclave to 30 atmospheres, autoclave The temperature was raised to 65 ° C, and while stirring, 5 g of ammonium persulfate dissolved in 90 g of ion-exchanged water and the monomer mixture placed in the pressure-resistant dropping tank were taken for 2 hours. The solution was added dropwise over the whole, and kept at the same temperature for 3 hours to complete the reaction. From the obtained product, an aqueous resin (C-4) having a nonvolatile content of 55 ° / ₀ , a _value of 1 to 1.6 of 1.6, and a solid content hydroxyl value of 5 Omg KOH / g was obtained.

 Examples 21 to 29

 In these examples, examples of a white paint composed of the polyisocyanate composition and the aqueous resin (C) are shown. In these examples, the aqueous resin (C-14) prepared in Reference Example 10 and the following aqueous resin (C-3) were used as the aqueous resin (C). The preparation method of the main components of the paint used for obtaining the white paint from the aqueous resins (C-3) and (C-14) and the polyisocyanate composition is shown below.

 • Aqueous resin (C-1-3)

 "Boncoat CG-5060" (Dainippon Ink and Chemicals, Inc.) Hydroxyl-containing acrylic resin emulsion, nonvolatile content 45%, solid content hydroxyl value 6 Omg KO

H / g).

 '' Preparation of paint main ingredient (Preparation of E-1)

 72.9 parts of deionized water, 6.F part of "Orotan SG-1" (pigment dispersant manufactured by Ichim & Haas Co., USA), 4.9 parts of 10% aqueous solution of sodium tripolyphosphate ,

2.2 parts of "Neugen EA-120" (wetting agent manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 18.0 parts of ethylene glycol, "Best Side 108 Fcho" [Dainippon Ink Chemical 1.0 part of preservative manufactured by Kogyo Co., Ltd., 0.5 part of ammonia water (2.8%), 249.2 part of "Titanics JR-600A" [titanium oxide manufactured by Tika Corporation] And a mixture consisting of 0.8 parts of “SN Deformer-1 121” (an antifoaming agent manufactured by San Nopco) was dispersed with a disper for about 1 hour. Add 607.0 parts of water-based resin (C-3), 38.2 parts of Texanol (a film-forming aid manufactured by Istman Chemical, USA), and 38.2 parts of Primal QR-708 1.2 parts of a 10% aqueous solution of “& Thickener manufactured by & Haas Co., Ltd.” and 0 2 parts of “BY K-028” [an antifoaming agent manufactured by BYK Chem. Paints with a weight concentration of 48% and a non-volatile content of 52.5% An agent component (E-1) was obtained.

 -Preparation of paint base component (Preparation of E-2)

 37.2 parts of ion-exchanged water, 0.7 parts of 25% ammonia water, 1.6 parts of “Neugen EA — 120” [wetting agent manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], “Tamol 73 1 6.4 parts of [pigment dispersant manufactured by Rohm & Haas, USA], 35.4 parts of ethylene glycol, 194.7 parts of Taipu CR-97 [titanium dioxide manufactured by Ishihara Sangyo Co., Ltd.] 9 parts of Best Side FX (preservatives manufactured by Dainippon Ink and Chemicals, Inc.), 1 and 4 parts of “Nobuco 8034” (antifoaming agent manufactured by San Nopco, Inc.), “Primal TT A mixture consisting of 33.2 parts of a 5% aqueous solution of [Rohm & Haas thickener], 33.2 parts of diethylene glycol dibutyl ether, and 655.3 parts of (C-14) was dispersed with a disperser. The mixture was uniformly dispersed for 1 hour to obtain a paint base component (II-2) having a pigment weight concentration of 35% and a nonvolatile content of 56%.

 -Preparation of water-based paints (F-1) to (F-9)

The water-based paints having a nonvolatile content of 52% were prepared by mixing the paint base components (成分 -1), (Ε-2), each of the polycarbonate compositions, and water at the ratios shown in Table 4. . In all Examples, the compounds were blended so that the molar ratio of the hydroxyl group in the isocyanate group aqueous resin (C-3, C-14) was 1.5Ζ1. Thus the white paint was prepared, following aqueous coating (F- 1) ~ (F- 9 ) and abbreviated _{(thus-obtained} water-based paint (F- 1) ~ (F- 9 ) , respectively Immediately after the preparation, a coating film was formed on a slide plate by the air spray method so that the dry film thickness was 70 m, and then dried for one week in an atmosphere at a temperature of 20 ° C and a humidity of 60% RH. Each cured coating film was evaluated for gloss and water resistance, and the evaluation results are shown in Table 4. Comparative Examples 8 and 9

 Each component shown in Table 4 was mixed at the ratio shown in the same table to prepare a comparative water-based paint. In these comparative examples, the aqueous resin containing isocyanate group (C-1

3) The compounding was performed so that the molar ratio of the hydroxyl groups in the mixture was 1.5: 1. The comparative water-based paints (RF-1) to (RF-2) obtained in this manner were treated in the same manner as in Example 2 "! -29" to give a dry film thickness of 70 / m on the plate immediately after preparation. Each of the resulting cured coatings was spray-coated and dried in the same manner as in the above example. The film was evaluated for gloss and water resistance. Table 4 shows the evaluation results.

Table 4

 Polyisocyanate Polyisosine Paint base ingredient

 IIIJ'J ノ J soil geometry / IIIJ'J ノ JM soil laughter Amount of water-based paint composition composition used Gloss

 Ft ¾Π swelling of retention [%] Dose rSRl “L¾oβΊJ

Example 2 1 F— 1 1 1 75 E— 1 500 86 84 〇 Example 22 F-2 Ρ-2 75 E- 1 500 9 1 90 ◎ Example 23 F- 3 Ρ-3 75 E- 1 500 92 9 1 ◎ Example 24 F— 4 -4 -4 75 E— 1 500 86 87 o Example 25 F- 5 Ρ-5 75 E- 1 500 84 83 〇 Example 26 F— 6 Ρ -6 75 E- 1 500 83 80 △ Example 27 F— 7 Ρ-790 E- 1 500 84 83 実 施 Example 28 F-8 Ρ— 8 90 E- 1 500 81 80 △ Example 29 F— 9 Ρ-9 80 E -2 500 81 93 ◎ Comparative Example 8 RF-1 R Ρ-1 8 1 E— 1 500 7 1 58 X Comparative Example 9 RF— 2 R Ρ-27 F E- 1 500 55 1 5 X

《Footnote to Table 4》

 Each numerical value indicating the usage ratio of raw materials shall be parts by weight. "Glossy":

 The appearance of the coating film was evaluated by the gloss value at which the coating film had a 60-degree specular reflectance [%].

 "water resistant" :

After immersing the slate plate coated with each water-based paint in deionized water at 25 ° C for 96 hours, the gloss retention and swelling state of the coating film were evaluated. The swelling of the coating film was visually evaluated according to the same evaluation criteria as in Examples 9 to 19. The gloss retention was calculated by the following equation. Gloss retention _[0/0] = (gloss value before gloss value Z deionized water immersion after deionized water immersion) X 1 00 Example 30

 An aqueous cured composition was prepared by mixing 100 parts of the water-dispersible polysocyanate composition (P-1) and 100 parts of deionized water. Hereinafter, this is referred to as an aqueous curable composition.

(G-1). Immediately after preparing the obtained aqueous curable composition (G-1), apply it on a glass plate and a PP plate using an applicator so that the coating film becomes 50 im. After drying for one week under the condition of humidity of 60% RH, a cured coating film was formed. The obtained cured coating film was evaluated for gel fraction and water resistance according to the same evaluation method and evaluation criteria as in Examples 9 to 17. Table 5 shows the evaluation results. Examples 31 to 37 and Comparative Examples 10 and 1 1

Aqueous curing was carried out in the same manner as in Example 30 except that 100 parts of the various polyisocyanate compositions shown in Table 5 were used instead of 100 parts of the polyisocyanate composition (P-1). A composition was prepared. Hereinafter, the compositions thus obtained are abbreviated as aqueous curable compositions (G-2) to (G-8), (RG-1) and (RG-2). Each of the aqueous curable compositions thus obtained was applied and dried on a glass plate and a PP plate immediately after preparation in the same manner as in Example 30 to form a cured coating film. For these, the same evaluation as in Example 30 was performed. Table 5 shows the evaluation results. Table 5

実施例 38

Example 38

 350 parts of the water-dispersible polyisocyanate composition (Ρ-1), 750 parts of deionized water, and 0.2 part of “ΒΥ Κ-028” (Β Υ ミ Chemical Company's defoamer) A water-based paint was prepared by mixing. Hereinafter, this is abbreviated as water-based paint (II-1). Immediately after preparing the obtained water-based paint (II-1), a coating film was formed on a gayal plate by an air spray method so that the dry film thickness became 3 O rn. Then, it was dried for one week under conditions of a temperature of 20 ° C and a humidity of 60% RH. The resulting cured coating film was evaluated for adhesion.

Immediately after preparation of the water-based paint (H-1), a coating film was formed on a slate plate by air-spray method so that the dry film thickness was 30 / m, and the temperature was 20 ° C and humidity was 60% RH. after drying for 24 hours at matter, as topcoat paint, _t was allowed painted by air spraying to a dry film thickness immediately after preparation of the aqueous coating (F- 1) of example 21 is 60 JU m then, the temperature 20 The sample was dried for 1 week under the conditions of ° C and a humidity of 60% RH. The multilayer cured coating film thus obtained was evaluated for adhesion. Table 6 shows the results of these evaluations.

Examples 39 to 45 and Comparative Examples 12 and 13 An aqueous solution was prepared in the same manner as in Example 38 except that 350 parts of the various polyisocyanate compositions shown in Table 6 were used instead of 350 parts of the polyisocyanate composition (P-1). A paint was prepared. Hereinafter, these are referred to as water-based paints (H-2) to (H-8),

(RH-1) and (RH-2). Each of the aqueous paints thus obtained was applied and dried on various substrates in the same manner as in Example 38, and then the aqueous paint of Example 21 was used as a top coat.

(F-1) was applied and dried to form a cured coating film. For these, the same evaluation as in Example 38 was performed. Table 6 shows the evaluation results. Table 6

《Footnote to Table 6》

 "Adhesiveness (1)":

Cuts were made at 2 mm intervals vertically and horizontally on the coating film formed on the gaical plate so that 25 grids of 2 mm square were formed using a pliers knife. Then, the cellophane adhesive tape was adhered to the grid, peeled off, and evaluated by the residual ratio, which is the ratio of the coating film remaining on the car board. The residual rate was calculated by the following equation. Residual rate of coating film [%] = (Area of coating film remaining after peeling Z Area of coating film on grid before peeling) X 100

 "Adhesiveness (2)":

 With respect to the multilayer coating film formed on the slate plate, the same operation as in the above-mentioned adhesion (1) was performed, and evaluated by the residual ratio which is the ratio of the coating film remaining on the slate plate. For this multi-layer coating film, there are both cases where only the top coat film is peeled off and cases where it is peeled off from the undercoat film.In both cases, it is considered that the coating film is peeled off and does not remain. The residual ratio was calculated in the same manner as in the case of "adhesion (1)". Example 46

95 parts of “H YD RAN HW— 3 1 1” (water dispersion of polyester-based urethane resin manufactured by Dainippon Ink and Chemicals, 45% non-volatile content), 95 parts of water-dispersible polyisocyanate composition (P— 5 parts of 1) were mixed and stirred to obtain an aqueous adhesive (K-1). The water-based adhesive (K-1) immediately after compounding was applied to a 2-mm thick plywood (JAS type II) by spraying at a ratio of 80 _g Zm ² and dried at 50 ° C for 5 minutes. A 2-mm-thick vinyl chloride sheet was laminated on the sheet and hot-pressed at 50 ° C and 0.01 MPa for one minute. Then, it was dried for one week at a temperature of 20 ° C and a humidity of 60 <½RH. With respect to the joined plate of the plywood thus obtained and the vinyl chloride sheet, the adhesiveness at 60 ° C. was evaluated. The evaluation results are shown in the column of “Adhesion evaluation (I)” in Table 7.

 Examples 4 to 53, Comparative Examples 1, 4, 1 5

 The aqueous adhesive (K) was prepared in the same manner as in Example 46 except that 5 parts of the various polysocyanate compositions shown in Table 7 were used instead of 5 parts of the polyisocyanate composition (P-1). —2) to (K-1 8), (RK-1) and (RK-2). A bonded plate of a plywood and a vinyl chloride sheet was prepared in the same manner as in Example 46 except that each of the aqueous adhesives thus obtained was used in place of the aqueous adhesive (II-1). These were evaluated for adhesiveness at 60 ° C. The evaluation results are shown in the column of “Adhesion evaluation (I)” in Table F.

-Change in adhesive properties over time after preparation of adhesive The aqueous adhesives obtained in Examples 46 to 53 and Comparative Examples 14 and 15 were allowed to stand at a temperature of 20 ° C and a humidity of 60% RH for 3 hours. A bonded plate was prepared in the same manner as in Example 46, and the adhesion at 60 ° C. was evaluated. The evaluation results are shown in the column of “Adhesion evaluation (II)” in Table 7. Even when the adhesives prepared in Examples 46 to 53 were used after 3 hours from the preparation, the decrease in adhesive strength was extremely small, and it was found that the aqueous adhesive of the present invention had a long pot life.

《Footnote to Table 7》

 "Adhesion evaluation (I), (II)":

A test piece was prepared by cutting the bonded board of plywood and vinyl chloride sheet to a width of 25 mm ₍ fix the plywood in a 60 ° C constant temperature bath, apply a load of 500 g to the vinyl chloride sheet, and leave it for 15 minutes. The peel length (mm) was measured at 180 degrees, and the smaller the value, the better the adhesiveness. Reference Example 1 1 [Preparation of NCO group-containing vinyl polymer (B)]

 The same container as in Reference Example 1 was charged with 429 parts of EDE, heated to 110 ° C under a nitrogen stream, and then heated to 400 parts of MP EGMA-1 and 2-isocyanatoethyl methacrylate (hereinafter, I EMA). A mixture of 500 parts of MMA, 500 parts of MMA, 45 parts of t-butylpropoxy-1-ethylhexanoate, and 5 parts of t-butylvinyloxybenzoate over 5 hours. did. After the dropwise addition, the mixture was reacted at 110 ° C for 9 hours to obtain a vinyl polymer solution having a nonvolatile content of 70% and a weight average molecular weight of 18,000. Hereinafter, this is abbreviated as a vinyl polymer (B-1). Table 8 shows the mixing ratio of the vinyl polymer (B-1). Table 8

実施例 54 〔水分散性ポリイソシァネート組成物 （P— 1 0) の調製〕 参考例 1 と同様の反応器に、 疎水性ポリイソシァネ一ト （A— 1 ) の 200部 と N CO基含有ビニル系重合体 （B— 1 ) の 1 00部を仕込み、 窒素気流下に 5 0°Cに昇温した後、 同温度で 1時間攪拌混合し、 不揮発分が 90%、 NCO基含 有率が 1 4. 6%なる水分散性ポリイソシァネート組成物を得た。 以下、 これを ボリイソシァネート組成物 （P— 1 0) と略称する。

Example 54 [Preparation of water-dispersible polyisocyanate composition (P-10)] In a reactor similar to that of Reference Example 1, 200 parts of hydrophobic polyisocyanate (A-1) and NCO groups were contained. 100 parts of the vinyl polymer (B-1) was charged, heated to 50 ° C under a nitrogen stream, and then stirred and mixed at the same temperature for 1 hour to obtain a nonvolatile content of 90% and an NCO group content. Was obtained in a water-dispersible polyisocyanate composition of 14.6%. Hereinafter, this is abbreviated as a polyisocyanate composition (P-10).

The obtained polyisocyanate composition was evaluated by the same evaluation method as in Examples 1 to 8 (Table 2-1) except for the residual ratio of the isocyanate group. Isocyanate group The value of the residual ratio was 3 hours after the preparation of the aqueous dispersion of the composition in the same manner as in Example 18. Table 9 shows the results of these evaluations. Table 9

実施例 5 5

Example 5 5

 The polyisocyanate composition (II-10) and the aqueous resin (C-11) were mixed such that the molar ratio of the isocyanate group and the hydroxyl group in the aqueous resin (C-11) was 1.21. An aqueous curable composition was prepared by mixing 43 parts of the polyisocyanate composition (II-10) and 500 parts of the aqueous resin (C-11). Hereinafter, this is referred to as an aqueous curable composition (D-10). Immediately after the preparation of the obtained aqueous curable composition (D-10), a glass plate and a polypropylene plate (hereinafter referred to as a PP plate) were prepared using an applicator so that the dry coating film became 60 m. This was applied on top and dried for one week at a temperature of 20 ° C and a humidity of 60% RH to form a cured coating film.

The obtained cured coating film was evaluated by the same evaluation method and evaluation criteria as in Example 9 19 (Table 3) except for the evaluation of the gel fraction and the water resistance. The evaluation results are shown in Table 10. Table 1 o

《Footnote to Table 10》

 "Gel fraction":

 The values were determined in the same manner as described in the footnote of Table 3, except that the time for immersing the coating film in acetone was changed to 24 hours.

 "water resistant" :

 The coating film formed on the glass plate was immersed in deionized water at 25 ° C for 48 hours, and the appearance of the coating film was evaluated according to the evaluation criteria shown in the footnote of Table 3. Example 5 6

 In this example, an example of a white paint comprising a polyisocyanate composition and an aqueous resin (C-11) will be described.

 -Preparation of water-based paint

Each of the water-based paints having a nonvolatile content of 52% was prepared by mixing the paint base component (E-1), the polyisocyanate composition, and water at the ratios shown in Table 11. In all the examples, the hydroxyl group in the isocyanate-based aqueous resin (C-11) was used. The compounding ratio was adjusted to 1.51. The white paint thus prepared is hereinafter referred to as a water-based paint (F-10).

 Immediately after preparation of the water-based paint (F-10) thus obtained, a coating film was formed on a slate plate by an air spray method so that the dry film thickness became 70 jtim. Then, it was dried for one week in an atmosphere of a temperature of 20 ° C and a humidity of 60% RH. Each of the obtained cured coating films was evaluated by the same evaluation method and evaluation standard as in Examples 21 to 29 (Table 4) except for the water resistance. The evaluation results are shown in Table 11. Table 11

《Footnote of Table 11》

 "water resistant" :

 The swelling state and gloss retention of the coating film after immersing the slide plate coated with the water-based paint (F-10) in deionized water at 25 ° for 48 hours were evaluated. The swelling of the coating film was evaluated according to the evaluation criteria shown in the footnote of Table 3. The gloss retention was calculated by the equation described in the footnote of Table 4. Example 57

100 parts of the water-dispersible polyisocyanate composition (P-10) and 1 part of deionized water The aqueous curable composition was prepared by mixing 00 parts. Hereinafter, this is referred to as aqueous curable composition (G-9). Immediately after preparation, the obtained aqueous curable composition (G-9) was applied on a glass plate and a PP plate using an applicator so that the dry coating film became 50 jum, and the temperature was 20 ° C. After drying for one week under the condition of humidity of 60% RH, a cured coating film was formed. The obtained cured coating film was evaluated for gel fraction and water resistance according to the same evaluation method and evaluation criteria as in Example 55 (Table 10). The evaluation results are shown in Table 12. Table 1 2

実施例 58

Example 58

 Mix 350 parts of the water-dispersible polyisocyanate composition (P-10), 750 parts of deionized water, and 0.2 part of ΓΒΥ Κ-028J (an antifoaming agent manufactured by BYK Chemie). To prepare an aqueous paint. Hereinafter, this is abbreviated as water-based paint (H-9). Immediately after the preparation of the obtained water-based paint (H-9), a coating film was formed on a calcium silicate plate by an air spray method so that a dry film thickness became 30 im. Then, it was dried at a temperature of 20 ° C. and a humidity of 60% RH for one week.

The resulting cured coating film was evaluated for adhesion. Immediately after the preparation of the water-based paint (H-9), a coating film was formed on a slate plate by the air spray method so that the dry film thickness was 30 m, and the temperature was 20 ° C and the humidity was 60%. After drying under RH conditions for 24 hours, the water-based paint (F-1) of Example 21 was applied by air spraying immediately after preparation so that the dry film thickness was 60 / m. Was. Then, at a temperature of 20 ° C, It was dried for one week under the condition of a humidity of 60% RH. The multilayer cured coating thus obtained was evaluated by the same evaluation methods and evaluation criteria as in Examples 38 to 45 (Table 6). Table 13 shows the results of these evaluations. Table 13

産業上の利用可能性

Industrial applicability

 The water-dispersible polyisocyanate composition of the present invention is excellent in dispersibility in water, stability in water, compatibility with an aqueous resin having an active hydrogen group-containing group, etc., and is a paint, an adhesive, and a fiber processing agent. The aqueous curable composition of the present invention is excellent in dispersibility in water, stability and curability in water, and gives a cured product excellent in appearance and water resistance. Useful for paints and waterborne adhesives.

Claims

The scope of the claims  1. A hydrophobic polyisocyanate (A) and a vinyl polymer (B) having a nonionic group and an isocyanate group, wherein the hydrophobic polyisocyanate (A) is converted to the nonionic in an aqueous medium. A water-dispersible polyisocyanate composition which can be dispersed with a vinyl polymer (B) containing a functional group and an isocyanate group. 2. The vinyl polymer (B) which is obtained by reacting a hydrophobic polyisocyanate with a vinyl polymer (b) having an active hydrogen group-containing group which reacts with a nonionic group and an isocyanate group. 2. The water-dispersible polysociate composition according to item 1 above. 3. The aqueous dispersion according to claim 1, wherein the ratio between the hydrophobic polyisocyanate (A) and the vinyl polymer (B) is 30: 70-85: 15 by weight. Polyisocyanate composition. 4. The water-dispersible polycisocyanate composition according to claim 1, wherein the vinyl polymer (B) has a hydrophobic group having a total carbon number of 4 or more. 5. The water-dispersible polyisocyanate composition according to claim 1, wherein the nonionic group is a polyoxyalkylene group having a terminal blocked with an alkoxy group. 6. The water-dispersible polyisocyanate composition according to claim 2, wherein the active hydrogen group-containing group is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an active methylene group. . 2. The water-dispersible polyisocyanate composition according to claim 1, wherein the vinyl polymer (B) contains a blocked active hydrogen group-containing grave and / or an epoxy group. 8. The water-dispersible polyisocyanate composition according to claim 7, wherein the blocked active hydrogen group-containing group is a hydroxyl group blocked with a triorganosilyl group. 9. Hydrophobic polyisocyanate and a vinyl polymer (b) containing an active hydrogen group-containing group that reacts with a nonionic group and an isocyanate group are combined with an isocyanate group and an active hydrogen group-containing group in a proportion of 3 to 35. Water dispersible polymer, characterized by reacting at a molar ratio of 0. , A method for producing a monolith composition. 10. The method for producing a water-dispersible polyisocyanate composition according to claim 9, wherein the vinyl polymer (b) has a hydrophobic group having a total carbon number of 4 or more. 11. The method for producing a water-dispersible polyisocyanate composition according to claim 9, wherein the nonionic group is a polyoxyalkylene group having a terminal capped with an alkoxy group. 12. The water-dispersible resin according to claim 9, wherein the active hydrogen group-containing group is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an active methylene group. A method for producing a fanate composition. 13. The method for producing a water-dispersible polyisocynate composition according to claim 9, wherein the vinyl polymer (b) contains a blocked active hydrogen group-containing group and / or an epoxy group. 14. The method for producing a water-dispersible polysocyanate composition according to claim 13, wherein the blocked active hydrogen group-containing group is a hydroxyl group blocked with a triorganosilyl group. 15. The water-dispersible polymer according to any one of claims 1 to 8. An aqueous curable composition comprising a nate composition and an aqueous resin (C) having an active hydrogen group-containing group that reacts with an isocyanate group. 1 6. An aqueous curable composition comprising the water-dispersible polyisocyanate composition according to any one of claims 1 to 8 and water. 1. An aqueous paint comprising the aqueous curable composition according to claim 15. 1 8. An aqueous paint comprising the aqueous curable composition according to claim 16. 9- An aqueous adhesive comprising the aqueous curable composition according to claim 15. 20. An aqueous adhesive comprising the aqueous curable composition according to claim 16.